Synthesis of Cuboctahedral CeO₂ Nanoclusters and Their Assembly into Cuboid Nanoparticles by Oriented Attachment

Abstract Here, we describe a simple approach to control the oriented attachment process through selective ligand scavenging from the {100} facets of CeO₂ nanoclusters. Aggregates of these nanoclusters smaller than 10 nm with controlled shapes and exposed facets were obtained. For the synthesis of the cuboctahedral CeO₂ nanoclusters, we developed a solvent‐controlled synthesis approach based on a non‐hydrolytic sol–gel process and used an ester aminolysis reaction to control ligand scavenging from the {100} facets. First‐principle calculations allowed us to understand and interpret, at the atomic level, the effects of shape control on the synthesis. Fine‐tuning of the desired morphologies can be achieved by controlling the values of the surface energies, which leads to the formation of morphologies that the classic growth process does not allow.